Positive active material layer for rechargeable lithium battery, separator for rechargeable lithium battery, and rechargeable lithium battery including at least one of same

ABSTRACT

A positive active material layer for a rechargeable lithium battery including a positive active material and a protection film-forming material is disclosed. A separator for a rechargeable lithium battery including a substrate and a porous layer positioned at least one side of the substrate and including a protection film-forming material is also disclosed. A rechargeable lithium battery can include at least one of the positive active material layer and the separator.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of and claims priority to U.S.application Ser. No. 14/086,869 filed Nov. 21, 2013 which claimspriority to and the benefit of Japanese Patent Application No.2012-256429 filed in the Japanese Patent Office on Nov. 22, 2012, andKorean Patent Application No. 10-2013-0100539 filed in the KoreanIntellectual Property Office on Aug. 23, 2013, the disclosures of whichare incorporated herein by reference in their entirety.

BACKGROUND

Field

This invention relates to a rechargeable lithium battery having apositive active material layer, a separator, or both

Description of the Related Technology

A rechargeable lithium battery has higher energy density than a leadbattery or a nickel cadmium battery and is widely used. However, therechargeable lithium battery often has a short cycle-life.

Japanese Patent Publication No. 2011-171293 discloses a method of usinga high dielectric solvent such as γ-butyrolactone, propylene carbonate,and the like, and simultaneously dissolving a lithium compound such aslithium tetracyanoborate (LiTCB) and the like in the high dielectricsolvent. In other words, the lithium compound such as lithiumtetracyanoborate (LiTCB) was used as an electrolyte for an electrolytesolution to improve cycle-life.

However, since the lithium compound is often present in a small amount,for example, 0.7 mol/L is dissolved in the high dielectric solvent, thebattery cycle-life improvement, for example under a current density of 1mA/cm², is insufficient. In addition, the high dielectric solvent mayprovide insufficient current density. In order to solve this problem,another method of dissolving the lithium compound in a low dielectricsolvent such as diethyl carbonate instead of a high dielectric solventhas been considered, but the lithium compound is not soluble in the lowdielectric solvent.

In addition, a rechargeable lithium battery has recently been used at anoperation voltage of greater than or equal to about 4.3V, but a lowoperation voltage is needed in a rechargeable lithium battery based onthe disclosure in the Japanese Patent Publication No. 2011-171293. ThisJapanese patent application discloses increasing the operation voltageof a rechargeable lithium battery by using an electrode with a lowpotential, for example, graphite as a negative electrode. However, thelithium compound is easily decomposed on the negative electrode.

Therefore, given the limited types of solvents and negative electrodesavailable, increasing the current density and the operation voltage of arechargeable lithium battery has been difficult.

SUMMARY OF CERTAIN INVENTIVE ASPECTS

One aspect of the disclosed technology relates to a positive activematerial layer for a rechargeable lithium battery having excellentcycle-life characteristics at a high current density and a high voltage.

Another aspect of the disclosure relates to a separator for arechargeable lithium battery having excellent cycle-life characteristicsat a high current density and a high voltage.

An additional aspect of the disclosure relates to a rechargeable lithiumbattery including at least one of the positive active material layer andthe separator.

One embodiment provides a positive active material layer for arechargeable lithium battery including the positive active material; andat least one protection film-forming material out of lithium compoundsrepresented by the following Chemical Formulae 4 to 6.LiB(CN)_(4-n1)(X₁)_(n1)  Chemical Formula 4LiP(CN)_(6-n2)(X₂)_(n2)  Chemical Formula 5LiC(CN)_(3-n3)(X₃)_(n3)  Chemical Formula 6

In the above Chemical Formulae 4 to 6,

n1 is an integer ranging from 0 to 3, n₂ is an integer ranging from 0 to5, n₃ is an integer ranging from 0 to 2, and X₁ to X₃ are independentlya ligand, wherein the ligand can be selected from a halogen atom, asubstituted or unsubstituted C₁-C₁₀ alkoxy group, a substituted orunsubstituted C₁-C₄ fluoroalkyl group, a linear carboxyl group, and asulfonyl group.

In some embodiments, the positive active material may include at leastone solid-solution oxide of compounds represented by the followingChemical Formulae 1 to 3.Li_(a)Mn_(x)Co_(y)Ni_(z)O₂  Chemical Formula 1

In the above Chemical Formula 1, 1.150≦a≦1.430, 0.45≦x≦0.6, 0.10≦y≦0.15,and 0.20≦z≦0.28.LiMn_(x)Co_(y)Ni_(z)O₂  Chemical Formula 2

In the above Chemical Formula 2, 0.3≦x≦0.85, 0.10≦y≦0.3, and 0.10≦z≦0.3.LiMn_(1.5)Ni_(0.5)O₄  Chemical Formula 3

In some embodiments, the protection film-forming material may beincluded in an amount of about 0.1 wt % to about 6 wt % based on thetotal amount of the positive active material layer.

When the protection film-forming material is a lithium compoundrepresented by the above Chemical Formula 4, the protection film-formingmaterial may be included in an amount of about 0.5 wt % to about 6 wt %based on the total amount of the positive active material layer. In someembodiments, when the protection film-forming material is a lithiumcompound represented by the above Chemical Formula 5, the protectionfilm-forming material may be included in an amount of about 0.3 wt % toabout 2 wt % based on the total amount of the positive active materiallayer. In some embodiments, when the protection film-forming material isa lithium compound represented by the above Chemical Formula 6, theprotection film-forming material may be included in an amount of about0.5 wt % to about 3 wt % based on the total amount of the positiveactive material layer.

In some embodiments, a separator for a rechargeable lithium battery caninclude a substrate; and a porous layer positioned at least one side ofthe substrate, wherein the porous layer includes at least one protectionfilm-forming material of lithium compounds represented by the aboveChemical Formulae 4 to 6.

The protection film-forming material may be included in an amount ofabout 10 wt % to about 90 wt % based on the total amount of the porouslayer.

In some embodiments, a rechargeable lithium battery can include apositive electrode including a current collector and positive activematerial layer disposed on the current collector and including apositive active material; a negative electrode; a separator including asubstrate and a porous layer positioned at least one side of thesubstrate; and an electrolyte, wherein at least one of the positiveactive material layer and the porous layer includes at least oneprotection film-forming material of lithium compounds represented by theabove Chemical Formulae 4 to 6.

The protection film-forming material is a material that forms aprotection film at the interface between the positive active materiallayer and the porous layer, or a material that forms a protection filmat an interface between the positive active material and the electrolytesolution.

In some embodiments, the protection film may include a polymer formed bypolymerization of the protection film-forming material.

The electrolyte may include a lithium salt, solvent and an additive, andthe additive may include a negative electrode-functioning compound, apositive-functioning compound, an ester-based compound, a carbonateester-based compound, a sulfuric acid ester-based compound, a phosphoricacid ester-based compound, a boric acid ester-based compound, acid ananhydride-based compound, an electrolyte-based compound, or acombination thereof.

Other embodiments are included in the following detailed description.

A rechargeable lithium battery having excellent cycle-lifecharacteristics at a high current density and a high voltage may berealized.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view showing the schematic structure of arechargeable lithium battery.

FIG. 2 is a graph showing a relationship between cycle number anddischarge capacity of rechargeable lithium battery cells according toExamples 1 and 2 and Comparative Example 1.

FIG. 3 is a graph showing a relationship between the addition amount ofa lithium compound and the discharge capacity of a rechargeable lithiumbattery cell.

FIG. 4 is a graph showing a relationship between the addition amount ofa lithium compound and the discharge capacity retention rate of arechargeable lithium battery cell.

FIG. 5 is a graph showing a relationship between cycle number anddischarge capacity of rechargeable lithium battery cells according toExamples 23 to 26 and Comparative Example 5.

FIG. 6 is a graph showing a relationship between cycle number anddischarge capacity of rechargeable lithium battery cells according toExamples 27 to 29 and Comparative Example 6.

DETAILED DESCRIPTION OF CERTAIN INVENTIVE EMBODIMENTS

Hereinafter, embodiments are described in detail. However, theseembodiments are exemplary, and this disclosure is not limited thereto.

Hereinafter, a rechargeable lithium battery according to one embodimentis described referring to FIG. 1.

As used herein, when specific definition is not otherwise provided, theterm “substituted” refers to one substituted with a substituent selectedfrom a halogen atom (F, Cl, Br, or I), a hydroxy group, a C₁ to C₂₀alkoxy group, a nitro group, a cyano group, an amine group, an iminogroup, an azido group, an amidino group, a hydrazino group, a hydrazonogroup, carbonyl group, carbamyl group, a thiol group, an ester group, anether group, a carboxyl group or a salt thereof, a sulfonic acid groupor a salt thereof, a phosphoric acid group or a salt thereof, a C₁ toC₂₀ alkyl group, a C₂ to C₂₀ alkenyl group, a C₂ to C₂₀ alkynyl group, aC₆ to C₃₀ aryl group, a C₃ to C₂₀ cycloalkyl group, a C₃ to C₂₀cycloalkenyl group, a C₃ to C₂₀ cycloalkynyl group, a C₂ to C₂₀heterocycloalkyl group, a C₂ to C₂₀ heterocycloalkenyl group, a C₂ toC₂₀ heterocycloalkynyl group, or a combination thereof, instead of atleast one hydrogen of a compound.

FIG. 1 is a cross-sectional view showing the schematic structure of arechargeable lithium battery.

Referring to FIG. 1, a rechargeable lithium battery 10 includes apositive electrode 20, a negative electrode 30, and a separator layer40. The separator layer 40 includes a separator 40 a and an electrolyte43. The positive electrode 20 includes a current collector 21 and apositive active material layer 22, and the separator 40 a includes asubstrate 41 and a porous layer 42 positioned on at least one side ofthe substrate 41.

In some embodiments, at least one of the positive active material layer22 and the porous layer 42 may include a protection film-formingmaterial. The protection film-forming material is described in thedescription of the positive active material layer 22 and the porouslayer 42 that will follow in detail.

The rechargeable lithium battery may have a charge cut-off voltage(oxidation reduction potential) (vs. Li/Li⁺⁾ of greater than or equal toabout 4.3V and less than or equal to about 5.0V and specifically,greater than or equal to about 4.5V and less than or equal to about5.0V.

The rechargeable lithium battery 10 has no particular limit regardingits shape and for example, may have a shape such as a cylinder, a prism,a laminated pouch type, a coin type, and the like.

The positive electrode 20 includes a current collector 21 and a positiveactive material layer 22.

The current collector 21 may be any conducting material including butnot limited to aluminum, stainless steel, nickel-plated steel, and thelike.

The positive active material layer 22 includes a positive activematerial and further includes a conductive material and a binder.

The positive active material may be, for example, a lithium-containingsolid-solution oxide, but is not particularly limited as far as amaterial electrochemically intercalates or deintercalates lithium ions.

In some embodiments, the solid-solution oxide may be at least one ofcompounds represented by the following Chemical Formulae 1 to 3.Li_(a)Mn_(x)Co_(y)Ni_(z)O₂  Chemical Formula 1

In the above Chemical Formula 1, 1.150≦a≦1.430, 0.45≦x≦0.6, 0.10≦y≦0.15,and 0.20≦z≦0.28.LiMn_(x)Co_(y)Ni_(z)O₂  Chemical Formula 2

In the above Chemical Formula 2, 0.3≦x≦0.85, 0.10≦y≦0.3, and 0.10≦z≦0.3.LiMn_(1.5)Ni_(0.5)O₄.  Chemical Formula 3

The positive active material may be included in an amount of about 85 wt% to about 96 wt % and preferably about 88 wt % to about 94 wt % basedon the total amount of the positive active material layer. When thecontent of the positive active material is included within the range,battery cycle life characteristics and energy density of a positiveelectrode may be increased. For example, energy density of the positiveelectrode may be increased up to about 530 Wh/l (180 Wh/kg) or more.

In some embodiments, the positive active material layer 22 may includethe protection film-forming material.

The protection film-forming material may form a protection film duringcharge of a rechargeable lithium battery and specifically, during itsfirst cycle charge. The protection film may pass lithium ions in theelectrolyte 43 and simultaneously suppress a solvent therein frompassing. The protection film-forming material, that is, the addition ofthe protection film-forming material, may improve battery cycle lifecharacteristics under a high current density and a high voltage.

The protection film-forming material may be a lithium compound includinga lithium ion, an negatively charged core atom, and a cyano groupcoordinated with the core atom. In other words, the protectionfilm-forming material may be a lithium salt of a lithium ion with ananion complex including a cyano group.

In some embodiments, the core atom may be selected from boron,phosphorus, and carbon.

The protection film-forming material may be specifically at least one oflithium compounds represented by the following Chemical Formulae 4 to 6.LiB(CN)_(4-n1)(X₁)_(n1)  Chemical Formula 4LiP(CN)_(6-n2)(X₂)_(n2)  Chemical Formula 5LiC(CN)_(3-n3)(X₃)_(n3)  Chemical Formula 6

In the above Chemical Formulae 4 to 6,

n₁ is an integer ranging from 0 to 3,

n₂ is an integer ranging from 0 to 5,

n₃ is an integer ranging from 0 to 2, and

X₁ to X₃ are a ligand except a cyano group, for example, a halogen atom,a substituted or unsubstituted C₁-C₁₀ alkoxy group, a substituted orunsubstituted C₁-C₄ fluoroalkyl group, a linear carboxyl group, asulfonyl group, and the like.

The positive active material has a crystal structure and thus, aplurality of active sites. The protection film-forming material aroundeach active site during the charge provides the active site withelectrons from isolated electrons of a nitrogen atom of the cyano group.Accordingly, when the nitrogen atom of the cyano group becomes a cationradical, the protection film-forming material is decomposed.

In addition, the active site may be supplied with one of electronsconsisted of the triple bond of the cyano group. The cation radical maynot only be adjacent with the active site but also, bonded with cyanogroups of other protection film-forming materials. Specifically, thecation radical attacks isolated electrons of the cyano group and may beattached to the cyano group. Accordingly, the protection film-formingmaterials themselves may be polymerized.

In some embodiments, the cation radical may attack the triple bond ofthe cyano group. When the other protection film-forming materials have aplurality of cyano groups, nitrogen atoms in free cyano groups may benew cation radicals. Then, the same polymerization reaction is repeatedand forms a polymer of the protection film-forming material on an activesite, that is, a protection film.

The protection film-forming material is decomposed and polymerized at alower potential than the decomposition of the solvent in theelectrolyte. In other words, the decomposition and polymerization of theprotection film-forming material may occur earlier than thedecomposition of the solvent. In this way, the protection film maysuppress the solvent from being passed.

However, the protection film may include an anion complex and may passlithium ions, since the lithium ions are inserted among the core atomsof the anion complex.

Accordingly, the protection film may pass the lithium ions in theelectrolyte but simultaneously suppress the solvent from be passed. Inother words, the protection film promotes the reaction of the activesites with the lithium ions during the charge after two cycles andsuppresses another reaction of the active sites with the solvent, thatis, decomposition of the solvent. Accordingly, battery cycle lifecharacteristics may be improved.

When the protection film-forming material includes more cyano groups,the protection film-forming material has a more complicated structureand simultaneously forms a protection film having a stable structure. Inaddition, the protection film-forming material may be hardly dissolvedin the solvent and less decomposed on the negative electrode.

Specifically, the n₁ and n₃ may be 0 in the above Chemical Formulae 4 to6, and the n₂ may be 3 in terms of a stereochemically structure. Since acomplex having a phosphorous element as a core atom has a rightoctahedron structure, the complex having three cyano groups may bestereochemically stable. In addition, when the n₁ to n₃ have the abovevalue, the cyano groups may be inserted among the core atoms andpositioned to be opposite one another and thus stabilize the protectionfilm.

The addition amount of the protection film-forming material may beincluded in an amount of about 0.1 wt % to about 6 wt % based on thetotal amount of the positive active material layer, and may be differentdepending on the composition of the protection film-forming material.When the protection film-forming material is include within the amountrange, the protection film-forming material may be suppressed from beingeluted into the electrolyte and may form a protection film having anappropriate thickness and thus suppress the solvent from being passedbut pass lithium ions.

In some embodiments, when the protection film-forming material is alithium compound represented by the above Chemical Formula 4, theprotection film-forming material may be included in an amount of about0.5 wt % to about 6 wt %, and preferably about 0.5 wt % to about 4 wt %based on the total amount of the positive active material layer.Specifically, the more cyano groups are included, the more lithiumcompounds represented by Chemical Formula 1 may be added. When aprotection film-forming material has more cyano groups, the less amountof the protection film-forming material may be dissolved in anelectrolyte, even though a large amount of the protection film-formingmaterial is included in the positive active material layer.

Specifically, w₁ indicating the upper amount limit of a lithium compoundrepresented by the above Chemical Formula 4 is 6, when n₁ is 0, and itis smaller, as the n₁ is larger. Specifically, when n₁ is 1, w₁ is 4,when n₁ is 2, w₁ is 3, and when n₁ is 3, w₁ is 2. In this way, as thenumber of cyano groups increases, the more protection film-formingmaterial may be added. As the number of cyano groups increased, the lessamount of the protection film-forming material may be dissolved in anelectrolyte even though a large amount of the protection film-formingmaterial is added in the positive active material layer.

Specifically, when n₁ is 0, the protection film-forming material may beincluded in an amount of greater than or equal to about 1 wt % and lessthan or equal to about 5 wt % and specifically, greater than or equal toabout 1.5 wt % and less than or equal to about 4 wt %. In addition, whenthe n₁ is 1, the protection film-forming material may be included in anamount of greater than or equal to about 0.7 wt % and less than or equalto about 2 wt %. When the protection film-forming material is includedwithin the range, battery cycle life characteristics may be improved.

In some embodiments, when the protection film-forming material is alithium compound represented by the above Chemical Formula 5, theprotection film-forming material may be included in an amount of about0.3 wt % to about 2 wt % based on the total amount of the positiveactive material layer. w₂ indicating the upper amount limit of thelithium compound represented by the above Chemical Formula 5 is 3, whenn₂ is 3, and the larger |3-n₂| is, the smaller the w2 may be.Specifically, when the |3-n₂| is 1, w2 is 2, when |3-n₂| is 2, w2 is1.5, and when |3-n₂| is 3, w₂ may be 1.0. The protection film-formingmaterial may be added in the maximum amount when n₂ is 3. The protectionfilm-forming material may be structurally stable, when the number of thecyano group is three.

When the protection film-forming material is a lithium compoundrepresented by Chemical Formula 6, the protection film-forming materialmay be included in an amount of about 0.5 wt % to about 3 wt % based onthe total amount of the positive active material layer. The w₃indicating the upper amount limit of the lithium compound represented bythe above Chemical Formula 6 is 3, when n₃ is 0, and the smaller the w₃is, the n₃ is larger. Specifically, when the n₃ is 1, the w3 is 2, whilewhen the n₃ is 2, the w₃ may be 1.

In this way, when there are more cyano groups, more protectionfilm-forming material may be included. As the number of cyano groupsincreases, less amount of the protection film-forming material may bedissolved in an electrolyte, even though a large amount of theprotection film-forming material is added in a positive active materiallayer.

The conductive material may include, for example, carbon black such asketjen black, acetylene black, and the like, natural graphite,artificial graphite, and the like but has no particular limit, as far asany material increases conductivity of a positive electrode.

The content of the conductive material may be about 3 wt % to about 10wt %, and specifically about 4 wt % to about 6 wt % based on the totalamount of the positive active material layer. When the conductivematerial is included within this range, battery cycle-lifecharacteristics and energy density may be improved.

The binder may include, for example, polyvinylidene fluoride, anethylene-propylene-diene terpolymer, a styrene-butadiene rubber, anacrylonitrile-butadiene rubber, a fluoro rubber, polyvinyl acetate,polymethylmethacrylate, polyethylene, nitrocellulose, and the like, buthas no particular limit and can include any material that binds thepositive active material and the conductive material on the currentcollector 21.

The binder may be included in a range of about 3 wt % to about 7 wt %,and specifically about 4 wt % to about 6 wt % based on total amount ofthe positive active material layer. When the amount of the binder fallswithin this range, the battery cycle-life characteristics and energydensity may be improved.

The density of the positive active material layer 22 is not particularlylimited, but may be in the range of about 2.0 g/cm³ to about 3.0 g/cm³,and specifically in the range of about 2.5 g/cm³ to about 3.0 g/cm³.When the density of the positive active material layer 22 is within therange, the positive active material particles are not destroyed, andthus damage on electrical contact among the particles does not occur,and the battery cycle life and energy density may be increased due to anincreased utilization rate of the positive active material.

In some embodiments, the density of the positive active material layer22 may be obtained by dividing the surface density of the positiveactive material layer 22 after the compression by the thickness of thepositive active material layer 22 after the compression.

The positive active material layer 22 may be manufactured as follow: forexample, the positive active material, the conductive material, and thebinder are dry-mixed to obtain a mixture, and the mixture and theprotection film-forming material are dry-mixed to obtain a dry mixture.Then, the dry mixture is dispersed in an organic solvent to prepare aslurry, and the slurry is applied on a current collector 21, followed bydrying and compressing the same. Alternatively, the mixture is dispersedto form slurry, and then the protection film-forming material isdissolved in the slurry. That is to say, a method of adding theprotection film-forming material to the positive active material layeris not limited.

In some embodiments, the organic solvent may be capable of dissolvingthe protection film-forming material. In this case, it may be uniformlydispersed in the positive active material layer. Such an organic solventmay be, for example, N-methyl-2-pyrrolidone, and the like.

The coating method may include any suitable method, for example, a knifecoating, a gravure coating, and the like.

In some embodiments, the positive electrode 20 may be manufactured bypressing the positive active material layer 22 using a presser andvacuum-drying the same.

The positive active material layer 22 may be applied on the currentcollector 21 along with carboxylmethyl cellulose (CMC) as a thickener inan amount of about 1/10 weight or more relative to the total amount ofthe binder.

The negative electrode 30 includes a current collector 31 and a negativeactive material layer 32.

The current collector 31 may be any conductor, for example, aluminum,stainless steel, nickel-plated steel, and the like.

The negative active material layer 32 may be any negative activematerial layer used in a rechargeable lithium battery. For example, thenegative active material layer 32 includes a negative active material,and additionally a binder.

The negative active material may be of no particular limit and may beany material that electrochemically intercalates or deintercalateslithium ions. For example, the negative active material may beartificial graphite, natural graphite, a mixture of artificial graphiteand natural graphite, natural graphite coated with artificial graphite,silicon, a silicon-containing alloy, silicon oxide, tin, atin-containing alloy, tin oxide, a mixture of silicon oxide and agraphite material, a mixture of tin oxide and a graphite material, atitanium oxide-based compound such as Li₄Ti₅O₁₂, and the like.

The silicon oxide may be represented by SiO_(x) (0≦x≦2).

The amount of the negative active material may be in the range of about90 wt % to about 98 wt % based on the total amount of the negativeactive material layer. When the amount of the negative active materialis within the range, the battery cycle life characteristics and energydensity may be increased.

In some embodiments, the conductive material may be the same as theconductive material of the positive active material layer.

The amount of the binder including the thickener may be in the range ofabout 1 wt % to about 10 wt % based on the total amount of the negativeactive material layer. When the amount of the binder including thethickener is within the range, the battery cycle life and energy densitymay be increased.

The density of the negative active material layer 32 has no particularlimit, but may be, for example, in the range of about 1.0 g/cm³ to about2.0 g/cm³. When the density of the negative active material layer 32 iswithin the range, the battery cycle life and energy density may beincreased.

The negative active material layer 32 may be formed, for example, bydispersing the negative active material and the binder in a solvent suchas N-methyl-2-pyrrolidone, water, and the like to prepare a slurry, andcoating the slurry on the current collector 31, followed by drying thesame. Subsequently, the negative active material layer 32 may becompressed by using a presser to provide the negative electrode 30.

The density of the negative active material layer 32 may be obtained bydividing the surface density of the negative active material layer 32after the compression by the thickness of the negative active materiallayer 32 after the compression.

The separator layer 40 a may include a substrate 41 and a porous layer42 positioned on at least one side of the substrate 41.

The substrate 41 may be composed of a material such as polyethylene,polypropylene and the like, and may include a plurality of first pores41 a.

In FIG. 1, the first pore 41 a has a spherical shape, but the first poremay have various shapes without limitation.

In some embodiments, the first pore may have a diameter of about 0.1 μmto about 0.5 μm. The diameter of the first pore may be a diameter whenthe first pore is considered to be a spherical shape.

The first pore may be measured by, for example, an auto porosimeter(AutoporeIV) (SHIMADZU Corporation, Kyoto, Japan). The measuring deviceis used, for example, to measure distribution of a diameter distributionof the first pore 41 a, and calculate a representative value of thediameter having the highest distribution.

In some embodiments, the diameter of the first pore 41 a present in thesurface layer of the substrate 41 may be measured using a scanningelectron microscope (JSM-6060, JEOL Ltd., Tokyo, Japan). The measuringdevice may measure the diameter of the first pores 41 a, for example, atthe surface layer.

In some embodiments, the substrate 41 may have a porosity of about 38volume % to about 44 volume %. When the porosity of the substrate iswithin this range, the battery cycle life may be increased. The porosityof the substrate 41 may be obtained by dividing the total volume of thefirst pore 41 a by the total volume of the substrate. The porosity ofthe substrate 41 may be measured using an auto porosimeter (AutoporeIV)(SHIMADZU Corporation, Kyoto, Japan).

In some embodiments, the substrate 41 may have a thickness in the rangeof about 6 μm to about 19 μm. When the substrate 41 has a thicknesswithin this range, the cycle-life is improved.

The porous layer 42 may be formed of a material different from thesubstrate 41, for example, a resin such as polyvinylidene fluoride,polyamideimide, aramid (aromatic polyamide), and the like. The porouslayer 42 may include a plurality of the second pores 42 a.

The second pores 42 a may have a spherical shape as shown in FIG. 1 butmay also have various other shapes.

The shape and size of the second pore 42 a may be different from thefirst pore 41 a.

Specifically, the diameter and porosity of the second pore 42 a may belarger than the first pore 41 a. In some embodiments, the second pore 42a may have a diameter of about 1 μm to about 2 μm.

The diameter of the second pore 42 a is a diameter when the second pore42 a is considered to have a spherical shape, and may be measured usinga scanning electron microscope JSM-6060 (JEOL Ltd., Tokyo, Japan).

Examples of polyvinylidene fluoride used in the porous layer 42 may beKF polymer#1700, #9200, #9300, and the like made by KUREHA Co, Tokyo,Japan.

The polyvinylidene fluoride may have a weight average molecular weightranging from about 500,000 to about 1,000,000.

The separator 40 a may have a porosity ranging from about 39% to about58%. When the separator 40 a has a porosity within this range, thebattery cycle life is increased.

Herein, the porosity of the separator 40 a may be obtained by dividingthe volume sum of the first pores 41 a and the second pores 42 a by thetotal volume of the separator 40 a, that is, the volume sum of the resinand the first pores 41 a of the substrate 41 and the resin and thesecond pores 42 a of the porous layer 42.

The porosity of the separator 40 a may be measured using an autoporosimeter (Autopore IV) (SHIMADZU Corporation, Kyoto, Japan).

Because the porosity of the separator 40 a is larger than the porosityof the substrate 41, the porosity of the porous layer 42, that is tosay, the porosity of the second pore 42 a is higher than the porosity ofthe substrate 41, that is to say, porosity of the first pore 41 a.

The thickness of the porous layer 42 may be in the range of about 1 μmto about 5 μm. The thickness of the separator 40 a, that is, thethickness sum of the substrate 41 and the porous layer 42, may be in therange of about 10 μm to about 25 μm. When the porous layer 42 and theseparator 40 a, respectively, have a thickness within the range,cycle-life characteristics may be increased.

The porous layer 42 may be formed on both sides of the substrate 41,that is, the side of the substrate 41 facing the positive electrode 20and the other side thereof facing the negative electrode 30, but is notlimited thereto. Specifically, the porous layer 42 may be positioned onone side of the substrate facing at least the negative electrode 30. Theporous layer 42 formed on both sides of the substrate 41 may bepreferable in order to increase the battery cycle life characteristicsof a rechargeable lithium battery.

The substrate 41 may have air permeation, specifically defined as JISP8117 standard, ranging from about 250 sec/100 cc to about 300 sec/100cc but is not limited thereto. The separator 40 a may have airpermeation ranging from about 220 sec/100 cc to about 340 sec/100 cc butis not limited thereto. When the substrate 41 and the separator 40 arespectively have air permeation within the range, the battery cyclelife may be increased.

The air permeation of the substrate 41 and the separator 40 a may bemeasured using a GURLEY air permeation meter G-B2 (Toyobesq Co. Ltd.,Tokyo, Japan).

The separator 40 a may be manufactured as follows.

A resin constituting the porous layer 42 and a water-soluble organicsolvent are mixed at a weight ratio of about 5 to 10:about 90 to 95 toprepare a coating liquid. The water-soluble organic solvent may be, forexample, N-methyl-2-pyrrolidone, dimethyl acetamide (DMAc), tripropyleneglycol (TPG), and the like.

Subsequently, the coating liquid is coated to be in the range of about 1μm to about 5 μm thick on both sides or one side of the substrate 41.Then, the coated substrate 41 is treated with a coagulation solution tocoagulate the resin in the coating solution. Herein, the method oftreating the coated substrate 41 with the coagulation solution may befor example, a method of dipping the coated substrate 41 in thecoagulation solution or strongly pouring the coagulation solution on thecoated substrate. Accordingly, the separator 40 a may be manufactured.

In some embodiments, the coagulation solution may be obtained by mixingthe water-soluble organic solvent with water.

In some embodiments, the water may be mixed in an amount of about 40volume % to about 80 volume % based on the total volume of thecoagulation solution.

Subsequently, the separator 40 a is rinsed with water and dried toremove water and the water-soluble organic solvent from the separator 40a.

In some embodiments, the porous layer 42 may include the aboveprotection film-forming material.

When the protection film-forming material is added to the porous layer,the protection film may be formed at the interface between the porouslayer 42 and the positive active material layer 22. Specifically, theprotection film-forming material may be added to the porous layer 42facing the positive electrode 20. The material contacting the positiveactive material layer of the protection film-forming material dispersedin the porous layer may be decomposed and polymerized during charging,and accordingly forms a protection film at the interface between theporous layer 42 and the positive active material layer 22. That is tosay, the protection film-forming material may form a protection film atthe interface between the positive active material and the electrolytesolution.

In some embodiments, the protection film may include a polymer formed bypolymerization of the protection film-forming material.

In addition, the protection film-forming material may be also added tothe porous layer 42 facing the negative electrode.

The protection film-forming material may be included in an amount ofabout 10 wt % to about 90 wt %, and about 40 wt % to about 90 wt % basedon the total amount of the porous layer. When the protectionfilm-forming material is within the range described herein, the amountcontacting the positive active material may increases, and the porosityof a porous layer may be easily controlled.

The separator may be formed by applying a coating solution, which mayinclude a resin constituting the porous layer, the protectionfilm-forming material and the water-soluble organic solvent on thesubstrate 41, solidifying the resin, and the removing the water-solubleorganic solvent. The water-soluble organic solvent may dissolve theprotection film-forming material.

In some embodiments, both the positive active material layer 22 and theporous layer 42 may include the above protection film-forming material.

When the protection film-forming material is added to the electrolyte orthe negative electrode, a protection film is hard to form and, when itis added to the negative electrode, it may decompose on the negativeelectrode, and accordingly the generated decomposition products may havean unfavorable effect on reactions on the negative electrode.

In some embodiments, the electrolyte 43 may include a lithium salt, asolvent, and an additive.

The lithium salt may be an electrolytic salt of the electrolyte 43.

The lithium salt may include LiPF₆, LiClO₄, LiBF₄, LiAsF₆, LiSbF₆,LiSO₃CF₃, LiN(SO₂CF₃)₂, LiN(SO₂CF₂CF₃)₂, LiC(SO₂CF₂CF₃)₃, LiC(SO₂CF₃)₃,LiI, LiCl, LiF, LiPF5(SO₂CF₃), LiPF₄(SO₂CF₃)₂, and the like. Among them,LiPF₆, LiClO₄, LiBF₄, LiAsF₆, LiSbF₆ and the like may be preferable. Thelithium salt may be dissolved singularly or as a mixture of two or more.

The lithium salt is dissolved in electrolyte 43, and the battery cyclelife of a rechargeable lithium battery may be increased.

The concentration of the lithium salt (a sum of a lithium salt when aplurality of a lithium salt is dissolved in the electrolyte) may be inthe range of about 1.15 mol/L to about 1.5 mol/L, and specifically about1.3 mol/L to about 1.45 mol/L. When the concentration of the lithiumsalt is within the range, the battery cycle life of a rechargeablelithium battery may be increased.

In some embodiments, the solvent may include fluorinated ether where atleast one of hydrogen is substituted with a fluorine atom.

In some embodiments, the fluorinated ether is an ether where hydrogen issubstituted with fluorine and may increase oxidation resistance.

Considering the charge voltage of a positive active material andresistance against a current density, examples of the fluorinated ethermay include but are not limited to 2,2,2-trifluoroethylmethylether,2,2,2-trifluoroethyldifluoromethylether,2,2,3,3,3-pentafluoropropylmethylether,2,2,3,3,3-pentafluoropropyldifluoromethylether,2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethylether,1,1,2,2-tetrafluoro ethylmethylether,1,1,2,2-tetrafluoroethylethylether, 1,1,2,2-tetrafluoroethylpropylether,1,1,2,2-tetrafluoroethylbutylether,1,1,2,2-tetrafluoroethylisobutylether, 1,1,2,2-tetrafluoroethylisopentylether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethylether,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether,hexafluoroisopropylmethylether, 1,1,3,3,3-pentafluoro-2-trifluoromethylpropylmethylether, 1,1,2,3,3,3-hexafluoropropylmethylether, 1,1,2,3,3,3-hexafluoropropylethylether,2,2,3,4,4,4-hexafluorobutyldifluoromethylether, and the like. These maybe used singularly or as a mixture of two or more.

The amount of the fluorinated ether may be in the range of about 10volume % to about 60 volume %, and specifically about 30 volume % toabout 50 volume % based on total volume of the solvent. When the amountof the fluorinated ether is within the above range, cycle-lifecharacteristics may furthermore be increased. The fluorinated ether haslower solubility to the protection film-forming material than carbonateethylene-based organic solvent, and thus elution of the protectionfilm-forming material into electrolyte solution may be suppressed.

In some embodiments, the solvent may further include ethylenemonofluorocarbonate.

The ethylene monofluorocarbonate may be included in an amount of about10 volume % to about 30 volume %, and specifically about 15 volume % toabout 20 volume % based on the total volume of the solvent. When theethylene monofluorocarbonate is included within the above range,cycle-life characteristics may be furthermore improved.

In some embodiments, the solvent may further include a non-aqueoussolvent used in a rechargeable lithium battery.

The additive may be a negative-functioning compound, apositive-functioning compound, an ester-based compound, a carbonateester-based compound, a sulfuric acid ester-based compound, a sulfurousacid ester-based compound, a phosphoric acid ester-based compound, aboric acid ester-based compound, an acid anhydride-based compound, anelectrolyte-based compound, and the like. These may be used singularlyor as a mixture of two or more.

The negative-functioning compound may be, for example, WCA-1, WCA-2,WCA-3, and the like manufactured by Central Glass Co., Ltd, Tokyo,Japan.

The positive-functioning compound may be, for example, lithiumbisfluorosulfonylimide (LiFSI) and the like.

The ester-based compound may be difluoromethyl acetate, diethyltrifluoroacetate, diethyl trifluoroacetate, vinyl acetate, difluoroethylacetate, 3-sulfolene, and the like.

The carbonate ester-based compound may be vinylene carbonate,vinylethylene carbonate, difluoroethylene carbonate, diallyl carbonate,2,5-dioxahexane dimethyl acid, 2,5-dioxahexanedioic acid diethyl ester,and the like.

The sulfuric acid ester-based compound or the sulfurous acid ester-basedcompound may be ethylene sulfite, dimethyl sulfite, dimethyl sulfate,ethylene sulfate, 1,3-propane sultone, 1,4-butane sultone, propenesultone, and the like.

The phosphoric acid ester-based compound may be trimethyl phosphoricacid, trioctyl phosphoric acid, trimethylsilyl phosphoric acid, and thelike.

The boric acid ester-based compound may be trimethyl boric acid,trimethylsilyl boric acid, and the like.

The acid anhydride-based compound may be succinic anhydride, allylsuccinic anhydride, ethane disulfonic anhydride, and the like.

The electrolyte-based compound may be lithium bis(oxalato-O,O′)borate,lithium difluoro(oxalato-O,O′)borate, lithiumdifluorobis(oxalato-O,O′)phosphate, and the like.

The amount of the additive may be in the range of about 0.01 wt % toabout 5.0 wt % based on the total amount of the electrolyte solution.When the additive is included within the range, cycle-lifecharacteristics may be improved.

The rechargeable lithium battery may be manufactured as follows.

The separator 40 a is disposed between the positive electrode 20 and thenegative electrode 30 to form an electrode assembly. When the porouslayer 42 is formed on only one side of the substrate 41, the negativeelectrode 30 faces the porous layer 42. Subsequently, the electrodeassembly is processed to have a desired shape, for example, a cylinder,a prism, a laminated pouch type, a coin type, and the like and then,inserted into the container. Then, the above electrolyte is injectedinto the container, so that the pore of the separator 40 a may beimpregnated with the electrolyte. Accordingly, a rechargeable lithiumbattery is manufactured.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. These examples, however, should not in any sensebe interpreted as limiting the scope of the present invention.

Furthermore, what is omitted in this disclosure may be sufficientlyunderstood by those who have knowledge in this field and will not beillustrated here.

Example 1 Manufacture of Positive Electrode

90 wt % of a solid-solution oxideLi_(1.20)Mn_(0.55)Co_(0.10)Ni_(0.15)O₂, 6 wt % of ketjen black, 4 wt %of polyvinylidene fluoride, and 1 part by weight of LiTCB (LiB(CN)₄)(based on 100 parts by weight of the solid-solution oxide, the ketjenblack and the polyvinylidene fluoride) were dispersed intoN-methyl-2-pyrrolidone to prepare a slurry. The slurry was coated anddried on an aluminum current collecting foil to form a positive activematerial layer. Subsequently, the positive active material layer wascompressed to manufacture a positive electrode. Herein, the positiveactive material layer had a density of 2.3 g/cm³.

Manufacture of Negative Electrode

96 wt % of artificial graphite and 4 wt % of a styrene-butadiene rubberwere dispersed into N-methyl-2-pyrrolidone to prepare slurry. The slurrywas coated and dried on an aluminum current collecting foil to form anegative active material layer. Subsequently, the negative activematerial layer was compressed to make a negative electrode. Herein, thenegative active material layer had a density of 1.45 g/cm³.

Manufacture of Separator

Aramid (poly[N,N′-(1,3-phenylene)isophthalamide], Sigma-Aldrich JapanK.K.) was mixed with a water-soluble organic solvent in a weight ratioof 5.5:94.5 to prepare a coating liquid. The water-soluble organicsolvent was prepared by mixing dimethyl acetamide and tripropyleneglycol in a weight ratio of 50:50.

In addition, a porous polyethylene film (a thickness of 13 μm, aporosity of 42 volume %) was used as a substrate.

The coating liquid was coated to be 2 μm thick on both sides of thesubstrate. Subsequently, the coated substrate was impregnated in acoagulation solution to coagulate a resin in the coating liquid tomanufacture a separator. Herein, the coagulation solution was preparedby mixing water, dimethyl acetamide, and tripropylene glycol in a weightratio of 50:25:25.

Subsequently, the separator was washed with water and dried to removewater and the water-soluble organic solvent.

Preparation of Electrolyte Solution

An electrolyte solution was prepared by mixing monofluoroethylenecarbonate (FEC), ethylene carbonate (EC), dimethyl carbonate (DMC), andHCF₂CF₂OCH₂CF₂CF₂H in a volume ratio of 15:5:45:35 and dissolvinglithium hexafluoro phosphate in a concentration of 1.00 mol/L in themixed solvent.

Manufacture of Rechargeable Lithium Battery Cell

The separator was disposed between the positive and negative electrodesto manufacture an electrode assembly. The electrode assembly wasinserted into a test container, and the electrolyte solution wasinserted therein to soak each pore of the separator in the electrolytesolution and to manufacture a rechargeable lithium battery cell.

Example 2

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using 1.6 parts by weight of lithiumdifluoro-O,O′-oxalatoborate based on 100 parts by weight of the solventto prepare the electrolyte solution.

Comparative Example 1

The rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using no LiTCB during themanufacture of a positive electrode.

Evaluation 1-1: Cycle-Life Characteristics

The rechargeable lithium battery cells according to Examples 1 and 2 andComparative Example 1 were charged and discharged, and their cycle-lifecharacteristics were evaluated. The results were provided in thefollowing Table 1 and FIG. 2.

Formation Process: the rechargeable lithium battery cells were constantcurrent charged up to a voltage of 3 V at 0.2 mA/cm² and allowed tostand for 12 hours. Accordingly, the LiTCB was decomposed andpolymerized to form a protection film. Then, the rechargeable lithiumbattery cells were constant current/constant voltage charged to avoltage of 4.65 V at 0.2 mA/cm² and constant current discharged to avoltage of 2.00 V at 0.2 mA/cm² as one charge and discharge cycle.

Cycle Step: the rechargeable lithium battery cells were constantcurrent/constant voltage charged to a voltage of 4.55V at 3 mA/cm² andconstant current discharged to a voltage of 2.40V, and the charge anddischarge cycle was 500 times repeated.

Then, a capacity retention was calculated as a percentage by dividingdischarge capacity at the 500th cycle by initial discharge capacity atthe first cycle.

The tests were all performed at 25° C.

The discharge capacity was measured by using a TOSCAT3000 instrument(Dongyang System Co., Ltd., Tokyo, Japan).

FIG. 2 is a graph showing a relationship between the cycle number anddischarge capacity of the rechargeable lithium battery cells accordingto Examples 1 and 2 and Comparative Example 1.

TABLE 1 Discharge capacity (mAh) Capacity initial capacity 500th cycleretention (%) Example 1 175 137 78 Example 2 175 160 91 ComparativeExample 1 175 123 70

Referring to Table 1 and FIG. 2, Example 1 using a protection filmshowed excellent cycle-life characteristics under high current densityand high voltage compared with Comparative Example 1. In addition,Example 2 showed that capacity retention was remarkably increased whenan additive was included in the electrolyte solution.

Examples 3 to 21

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using LiTCB in various amountsprovided in the following Table 2 to manufacture the positive electrodein Example 1.

In addition, a rechargeable lithium battery cell was manufacturedaccording to the same method as Example 1 except for usingLiB(CN)₃(OCH₃) (LiMCB) in various amounts instead of the LiTCB tomanufacture the positive electrode in Example 1.

In addition, another rechargeable lithium battery cell was manufacturedaccording to the same method as Example 1 except for usingLiB(CN)₃(OCH₂CH₃) (LiECB) in various amounts provided in the followingTable 2 instead of the LiTCB to manufacture the positive electrode inExample 1.

TABLE 2 Protection film-forming material LiTCB LiMCB LiECB Amount 0.5parts by weight   Example 3 Example 10 Example 16 0.7 parts by weight  Example 4 Example 11 Example 17 1 parts by weight Example 1 Example 12Example 18 1.5 parts by weight   Example 5 Example 13 Example 19 2 partsby weight Example 6 Example 14 Example 20 3 parts by weight Example 7Example 15 Example 21 5 parts by weight Example 8 — — 6 parts by weightExample 9 — —

a part by weight in Table 2 is a unit based on 100 parts by weight ofthe total weight of the solid-solution oxide, the ketjen black, and thepolyvinylidene fluoride.

Evaluation 1-2: Cycle-Life Characteristics

The capacity retention (%) of the rechargeable lithium battery cellsaccording to Examples 3 to 21 was provided in the following Table 3 andFIGS. 3 and 4 by evaluating the battery cycle life characteristics ofthe rechargeable lithium battery cells according to Examples 3 to 21according to the same method as Evaluation 1-1. Herein, the capacityretention (%) was obtained as a percentage of discharge capacity at the500th cycle relative to initial capacity. The LiTCB, LiMCB, and LiECBall showed initial capacity of 175 mAh.

FIG. 3 is a graph showing the relationship between the amount of alithium compound added and the discharge capacity of the rechargeablelithium battery cells, and FIG. 4 is a graph showing the relationshipbetween the amount of the lithium compound added and discharge capacityretention of the rechargeable lithium battery cells.

TABLE 3 Discharge capacity (mAh) initial capacity 500th cycle Capacityretention (%) Example 1 175 137 78 Example 3 175 128 73 Example 4 175130 74 Example 5 175 140 80 Example 6 175 141 81 Example 7 175 142 81Example 8 175 140 80 Example 9 175 127 73 Example 10 175 127 73 Example11 175 132 75 Example 12 175 136 78 Example 13 175 137 78 Example 14 175136 78 Example 15 175 130 74 Example 16 175 127 73 Example 17 175 130 74Example 18 175 134 77 Example 19 175 134 77 Example 20 175 132 75Example 21 175 128 73

Referring to Table 3 and FIGS. 3 and 4, the rechargeable lithium batterycell using LiTCB as a protection film-forming material showed the mostincreased cycle-life characteristics. The LiTCB had a structurecontaining a cyano group as all the ligands and thus formed a stableprotection film. In addition, the LiTCB might be used in an amount of0.5 wt % to 6 wt %, and the LiMCB or LiECB might be used in an amount of0.5 wt % to 4 wt %.

Comparative Example 2

A rechargeable lithium battery cell was manufactured according to thesame method as Comparative Example 1 except for using 0.02 mol/l ofLiECB to prepare the electrolyte solution instead of those as describedin the procedure for Comparative Example 1.

Evaluation 1-3: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellaccording to Comparative Example 2 was evaluated according to the samemethod as Evaluation 1-1, and the results are provided in the followingTable 4.

TABLE 4 Discharge capacity (mAh) Capacity initial capacity 500th cycleretention (%) Comparative Example 2 160 80 50

Referring to Table 4, the electrolyte solution including a protectionfilm-forming material exhibited deteriorated cycle-life characteristics.The reason is that the protection film-forming material was dissolved inthe electrolyte solution and decomposed on the negative electrode andthus hindered reactions on the negative electrode.

On the other hand, when the cyano group of an anion complex issubstituted with other ligands such as in compounds like LiECB andLiTCB, LiECB was dissolved in the solvent, but the LiTCB was not almostdissolved therein.

Comparative Example 3

A rechargeable lithium battery cell was manufactured according to thesame method as Comparative Example 1 except for using 0.5 parts byweight of LiTCB (100 parts by weight of the artificial graphite and thestyrene-butadiene rubber) to manufacture the negative electrode asdescribed in the procedure of in Comparative Example 1.

Evaluation 1-4: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellaccording to Comparative Example 3 were evaluated according to the samemethod as Evaluation 1-1, and the results are provided in the followingTable 5.

TABLE 5 Discharge capacity (mAh) Capacity initial capacity 500th cycleretention (%) Comparative Example 3 159 0 0

Referring to Table 5, when the negative active material layer included aprotection film-forming material, cycle-life characteristics weredeteriorated. The reason is that the protection film-forming materialdecomposed on the negative electrode and hindered the reaction thereon.

Example 22

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using no LiTCB to manufacture thepositive electrode and adding polyvinylidene fluoride and LiTCB in aweight ratio of 40:60 to prepare a coating liquid for a separator inExample 1.

Comparative Example 4

The rechargeable lithium battery cell was manufactured according to thesame method as Comparative Example 1 except for adding polyvinylidenefluoride and Al₂O₃ in a weight ratio of 40:60 to prepare a coatingliquid for a separator as described in the procedures of ComparativeExample 1.

Evaluation 1-5: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellsaccording to Example 22 and Comparative Example 4 were evaluatedaccording to the same method as Evaluation 1-1, and the results areprovided in the following Table 6.

TABLE 6 Discharge capacity (mAh) Capacity initial capacity 500th cycleretention (%) Example 22 175 130 74 Comparative Example 4 175 123 70

Referring to Table 6, even when a protection film-forming material wasincluded in a porous layer, the battery cycle-life characteristics wereincreased by a protection film.

Examples 23 to 26

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for adding LiPF₃(CN)₃ in various amountsprovided in the following Table 7 instead of the LiTCB to manufacture apositive electrode and lithium hexafluoro phosphate in a concentrationof 1.2 mol/L to prepare the electrolyte solution as described in theprocedures of Example 1.

Evaluation 1-6: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellsaccording to Examples 23 to 26 were evaluated according to the samemethod as Evaluation 1-1, and the results are provided in the followingTable 7 and FIG. 5.

FIG. 5 is a graph showing the relationship between the cycle number andthe discharge capacity of the rechargeable lithium battery cellsaccording to Examples 23 to 26.

TABLE 7 Discharge Amount of capacity (mAh) LiPF₃(CN)₃ initial Capacity(parts by weight) capacity 500th cycle retention (%) Example 23 0.3 180139 77 Example 24 0.7 180 148 82 Example 25 1.0 178 143 80 Example 263.0 177 137 77

A part by weight in Table 7 is used based on 100 parts by weight of thetotal weight of the solid-solution oxide, ketjen black, andpolyvinylidene fluoride.

Referring to Table 7 and FIG. 5, LiPF₃(CN)₃ as the protectionfilm-forming material decomposed and polymerized, forming a protectionfilm, and this protection film increased cycle-life characteristicsunder high current density and high voltage.

Examples 27 to 29

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for substituting LiC(CN)₄ in variousamounts provided in the following Table 8 instead of the LiTCB tomanufacture the positive electrode and lithium hexafluoro phosphate in aconcentration of 1.2 mol/L to prepare the electrolyte solution inExample 1.

Evaluation 1-7: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellsaccording to Examples 27 to 29 were evaluated according to the samemethod as Evaluation 1-1, and the results are provided in the followingTable 8 and FIG. 6.

FIG. 6 is a graph showing the relationship between cycle number anddischarge capacity of the rechargeable lithium battery cells accordingto Examples 27 to 29.

TABLE 8 Discharge Amount of capacity (mAh) LiC(CN)₃ initial Capacity(parts by weight) capacity 500th cycle retention (%) Example 27 0.5 180137 76.1 Example 28 1.0 180 143 79 Example 29 3.0 176 141 80

Referring to Table 8 and FIG. 6, the LiC(CN)₃ as a protectionfilm-forming material was decomposed and polymerized to from aprotection film, and the protection film increased cycle-lifecharacteristics under a high current density and high voltage.

Examples 30 to 34

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using LiB(CN)₂(OCH₃)₂ in variousamounts provided in the following Table 9 instead of the LiTCB tomanufacture the positive electrode as described in the procedures ofExample 1.

In addition, a rechargeable lithium battery cell was manufacturedaccording to the same method as Example 1 except for using LiBCN(OCH₃)₃in various amounts provided in the following Table 9 instead of theLiTCB to manufacture the positive electrode as described in theprocedures of Example 1.

TABLE 9 Protection film-forming material LiB(CN)₂(OCH₃)₂ LiBCN(OCH₃)₃Amount 0.5 parts by weight Example 30 Example 33 0.7 parts by weightExample 31 Example 34   1 parts by weight Example 32 —

Evaluation 1-8: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellsaccording to Examples 30 to 34 were evaluated according to the samemethod as Evaluation 1-1, and the results are provided in the followingTable 10.

TABLE 10 Discharge capacity (mAh) initial capacity 500th cycle Capacityretention (%) Example 30 180 141 78 Example 31 180 140 78 Example 32 180135 75 Example 33 180 139 77 Example 34 180 138 77

Referring to Table 10, the LiB(CN)₂(OCH₃)₂ and LiBCN(OCH₃)₃ as aprotection film-forming material decomposed and polymerized to form aprotection film, and this protection film increased the cycle-lifecharacteristics under a high current density and a high voltage.

Examples 35 to 47

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using LiPF₂(CN)₄ in various amountsprovided in the following Table 11 instead of the LiTCB to manufacturethe positive electrode as described in the procedures of Example 1.

In addition, a rechargeable lithium battery cell was manufacturedaccording to the same method as Example 1 except for using LiPF(CN)₅ invarious amounts provided in the following Table 11 instead of the LiTCBto manufacture the positive electrode as described in the procedures ofExample 1.

Furthermore, a rechargeable lithium battery cell was manufacturedaccording to the same method as Example 1 except for using LiP(CN)₆ invarious amounts provided in the following Table 11 instead of the LiTCBto manufacture the positive electrode as described in the procedures ofExample 1.

TABLE 11 Protection film-forming material LiPF₂(CN)₄ LiPF(CN)₅ LiP(CN)₆Amount 0.3 parts by weight Example 35 — — 0.5 parts by weight Example 36Example 41 Example 45 0.7 parts by weight Example 37 Example 42 Example46   1 part by weight Example 38 Example 43 Example 47 1.5 parts byweight Example 39 Example 44 —   2 parts by weight Example 40 — —

Evaluation 1-9: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellsaccording to Examples 35 to 47 were evaluated according to the samemethod as Evaluation 1-1, and the results are provided in the followingTable 12.

TABLE 12 Discharge capacity (mAh) initial capacity 500th cycle Capacityretention (%) Example 35 180 141 78 Example 36 180 148 82 Example 37 180149 83 Example 38 180 153 85 Example 39 180 144 80 Example 40 180 137 77Example 41 180 151 84 Example 42 180 157 87 Example 43 180 160 89Example 44 180 149 83 Example 45 180 151 84 Example 46 180 166 92Example 47 180 157 87

Referring to Table 12, the LiPF₂(CN)₄, LiPF(CN)₅, and LiP(CN)₆ as aprotection film-forming material decomposed and polymerized to form aprotection film, and this protection film increased cycle-lifecharacteristics under a high current density and a high voltage.

Examples 48 to 53

A rechargeable lithium battery cell was manufactured according to thesame method as Example 1 except for using LiC(CN)₂OCH₃ in variousamounts as provided in the following Table 13 instead of the LiTCB tomanufacture the positive electrode as described in the procedures ofExample 1.

In addition, a rechargeable lithium battery cell was manufacturedaccording to the same method as Example 1 except for using LiCCN(OCH₃)₂in various amounts as provided in the following Table 13 instead of theLiTCB to manufacture the positive electrode as described in theprocedures of Example 1.

TABLE 13 Protection film-forming material LiC(CN)₂OCH₃ LiCCN(OCH₃)₂Amount 0.5 parts by weight Example 48 Example 52 0.7 parts by weightExample 49 —   1 parts by weight Example 50 Example 53 1.5 parts byweight Example 51 —

Evaluation 1-10: Cycle-Life Characteristics

The cycle-life characteristics of the rechargeable lithium battery cellsaccording to Examples 48 to 53 were evaluated using the same method asEvaluation 1-1, and the results are provided in the following Table 14.

TABLE 14 Discharge capacity (mAh) initial capacity 500th cycle Capacityretention (%) Example 48 180 148 82 Example 49 180 142 79 Example 50 180140 78 Example 51 180 140 78 Example 52 180 145 81 Example 53 180 141 78

Referring to Table 14, LiC(CN)₂OCH₃ and LiCCN(OCH₃)₂ as a protectionfilm-forming material decomposed and were polymerized to form aprotection film, and this protection film increased the cycle-lifecharacteristics under a high current density and a high voltage.

While this disclosure has been described in connection with what ispresently considered to be practical exemplary embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

What is claimed is:
 1. A rechargeable lithium battery, comprising apositive electrode comprising a current collector and positive activematerial layer disposed on the current collector and including apositive active material; wherein the positive active material comprisesat least one solid-solution oxide of compounds represented by thefollowing Chemical Formulae 1 to 3:Li_(a)Mn_(x)Co_(y)Ni_(z)O₂  Chemical Formula 1 wherein, 1.150≦a≦1.430,0.45≦x≦0.6, 0.10≦y≦0.15, and 0.20≦z≦0.28,LiMn_(x)Co_(y)Ni_(z)O₂  Chemical Formula 2 wherein, 0.3≦x≦0.85,0.10≦y≦0.3, and 0.10≦z≦0.3,LiMn_(1.5)Ni_(0.5)O₄;  Chemical Formula 3 a negative electrode; aseparator including a substrate and a porous layer positioned on atleast one side of the substrate; and an electrolyte solution, wherein atleast one of the positive active material layer and the porous layercomprises at least one protection film forming material of lithiumcompounds represented by the following Chemical Formulae 5 or 6:LiP(CN)_(6-n2)(X₂)_(n2)  Chemical Formula 5LiC(CN)_(3-n3)(X₃)_(n3)  Chemical Formula 6 wherein, n₂ is an integerranging from 0 to 5, n₃ is an integer ranging from 0 to 2, and X₂ and X₃are independently selected from a halogen atom, a substituted orunsubstituted C₁-C₁₀ alkoxy group, a substituted or unsubstituted C₁-C₄fluoroalkyl group, a linear carboxyl group, and a sulfonyl group.
 2. Therechargeable lithium battery of claim 1, wherein the protectionfilm-forming material is a material that forms a protection film at aninterface between the positive active material layer and the porouslayer.
 3. The rechargeable lithium battery of claim 1, wherein theprotection film-forming material is a material that forms a protectionfilm at an interface between the positive active material and theelectrolyte solution.
 4. The rechargeable lithium battery of claim 2,wherein the protection film comprises a polymer formed by polymerizationof the protection film-forming material.
 5. The rechargeable lithiumbattery of claim 3, wherein the protection film comprises a polymerformed by polymerization of the protection film-forming material.
 6. Therechargeable lithium battery of claim 1, wherein when the positiveactive material layer comprises the protection film-forming material,the amount of the protection film-forming material is in the range ofabout 0.1 wt % to about 6 wt % based on the total amount of the positiveactive material layer.
 7. The rechargeable lithium battery of claim 6,wherein when the protection film-forming material is a lithium compoundrepresented by the above Chemical Formula 5,LiP(CN)_(6-n2)(X₂)_(n2)  Chemical Formula 5: the amount of theprotection film-forming material is in the range of about 0.3 wt % toabout 2 wt % based on the total amount of the positive active materiallayer, and when the protection film-forming material is a lithiumcompound represented by the above Chemical Formula 6,LiC(CN)_(3-n3)(X₃)_(n3)  Chemical Formula 6: the amount of protectionfilm-forming material is in the range of about 0.5 wt % to about 3 wt %based on the total amount of the positive active material layer.
 8. Therechargeable lithium battery of claim 1, wherein when the porous layercomprises the protection film-forming material, the amount of theprotection film-forming material is in the range of about 10 wt % toabout 90 wt % based on the total amount of the porous layer.
 9. Therechargeable lithium battery of claim 1, wherein the electrolytesolution comprises a lithium salt, solvent and an additive, and theadditive comprises a negative-functioning compound, apositive-functioning compound, an ester-based compound, a carbonateester-based compound, a sulfuric acid ester-based compound, a phosphoricacid ester-based compound, a boric acid ester-based compound, an acidanhydride-based compound, or a combination thereof.